3278 Chem. Mater.

2007, 19, 3278-3285

Synthesis and VUV Photoluminescence Characterization of

(Y,Gd)(V,P)O4:Eu3+ as a Potential Red-emitting PDP Phosphor
Chia-Chin Wu,†,‡ Kuei-Bo Chen,§ Chi-Sen Lee,§ Teng-Ming Chen,*,† and
Bing-Ming Cheng#
Phosphor Research Laboratory and Applied Solid-State Laboratory, Department of Applied Chemistry,
National Chiao Tung UniVersity, Hsinchu 30010, Taiwan, Materials and Chemical Research Laboratories,
Industrial Technology Research Institute, Hsinchu, 30040 Taiwan, and National Synchrotron Radiation
Research Center, Hsinchu Science Park, Hsinchu 30076, Taiwan
ReceiVed May 5, 2006. ReVised Manuscript ReceiVed March 6, 2007

YVO4:Eu3+-basedphosphorsinthreeserieswithcompositions(Y1-xEux)(V1-zPz)O4,(Y0.95-yGdyEu0.05)(V0.4P0.6)O4
and (Y0.95-yEu0.05Gdy)(V1-zPz)O4 were synthesized and investigated as potential red-emitting phosphors
for a plasma display panel (PDP). The optimal substitution proportions of P for V and Gd for Y were
determined to be 60 and 20 mol %, respectively, for (Y0.95-yGdy)(V1-zPz)O4 doped with 5 mol %
Eu3+. The vacuum ultraviolet PL and PLE spectra and chromaticity characteristics for the synthesized
phosphors were measured and compared against those of a commercial red-emitting phosphor. Pumping
the (Y,Gd)(P,V)O4:Eu3+ phosphors at a wavelength of 172 nm is more efficient than that at 147 nm. For
VUV excitation at 147 nm, the CIE chromaticity coordinates for our red-emitting (Y1-yGdy)(V0.4P0.6)-
O4:Eu3+ are (0.6614,0.3286), as compared to (0.6443, 0.3613) for (Y,Gd)BO3:Eu3+ from Kasei Optonix
Ltd. We suggest that the composition-optimized (Y0.75Gd0.20Eu0.05)(V0.4P0.6)O4 can serve as an alternative
phosphor to replace a widely used red-emitting commercial phosphor such as (Y,Gd)BO3: Eu3+ or
Y2O3: Eu3+.

1. Introduction and saturation, and decay lifetime of PDP phosphors have

A plasma display panel (PDP) has become regarded as a
promising candidate for a display with a large area mainly
because its emissive features include a wide viewing angle
and high brightness. PDP phosphors are expected to meet
the critical requirements to yield a high luminous efficiency
on excitation with vacuum ultraviolet (VUV) radiation of
wavelengths 147 and 172 nm generated from a plasma of a
mixture of He and Xe noble gases. To improve the
performance of PDP, we investigated the development of
efficient VUV-excitable phosphors. Oxide phosphors with
aluminate, silicate, vanadate, phosphate, and borate groups
generally exhibit strong absorption in the VUV spectral
region.1-3 The main weaknesses of commercial phosphors
in current use are the lack of color purity of a red-emitting
phosphor such as (Y,Gd)BO3:Eu3+, a long decay lifetime
of green-emitting phosphors such as Zn2SiO4:Mn2+ and
BaAl12O19:Mn2+, and color degradation attributed to material
instability of a blue-emitting phosphor such as BaMgAl10O17:
Eu2+. For these reasons, the optical and luminescence
properties such as luminous efficiency, purity of chromaticity
been widely investigated.4-6
Being considered as a red-emitting phosphor, (Y,Gd)BO3:
Eu3+ is well-known as a PDP phosphor because of its high
luminous efficiency under VUV excitation at 147 nm.
However, its main emission appearing at 593 nm and
attributed to Eu3+ yields poor and unsaturated red color
chromaticity. The red emission attributed to the transition
5D f 7F of Eu3+ is hypersensitive to the lattice symmetry
0 2
of the host matrix, and its luminescent intensity is expected
to be strong if the symmetry of the crystal is lowered.7 The
Eu3+ ion occupies a lattice site with inversion symmetry in
(Y,Gd)BO3:Eu3+; the transition 5D0 f 7F1 (593 nm) thus
predominates.8 Furthermore, the well-known phosphor Eu3+-
activated Y(P,V)O4 used for high-pressure mercury lamps
has been reinvestigated and evaluated as an alternative
phosphor for PDP application as it exhibits a greater color
saturation in the red with color coordinates (0.66, 0.33) than
that with coordinates (0.65, 0.36) of conventional (Y,Gd)-
BO3:Eu3+.9 A quest for red-emitting PDP phosphors with
improved efficiency, brightness, and color saturation has

* To whom correspondence should be addressed. Tel: 886 35731695. Fax:
886 35723764. E-mail: tmchen@mail.nctu.edu.tw.
† Phosphor Research Laboratory, National Chiao Tung University.
‡ Materials and Chemical Research Laboratories, Industrial Technology
Research Institute.
§ Applied Solid-State Laboratory, National Chiao Tung University.
# National Synchrotron Radiation Research Center, Hsinchu Science Park.
(1) Justel, T.; Krupa, J. C.; Wiechert, D. U. J. Lumin. 2001, 93, 179.
(2) Koike, J.; Kojima, T.; Toyanaga, R.; Kagami, A.; Hase, T.; Inaho, H.
J. Electrochem. Soc. 1979, 126, 1008.
(3) de Jager-Veenis, A. W.; Bril, A. J. Electrochem. Soc. 1976, 123, 1253.
(4) Okazaki, C.; Shiiki, M.; Suzuki, T.; Suzuki, K. J. Lumin. 2000, 87,
1280.
(5) Yokota, K.; Zhang, S. X.; Kimura, K.; Sakamoto, A. J. Lumin. 2001,
92, 223.
(6) Lu, S. W.; Copealand, T.; Lee, B. I.; Tong, W.; Wagner, B. K.; Park,
W.; Zhang, F. J. Phys. Chem. Solids 2001, 62, 777.
(7) Shionoya, S.; Yen, W. M. Phosphor Handbook; CRC Press: Boca
Raton, FL, 1999; p 190.
(8) Wang, Y.; Endo, T.; He, L.; Wu, C. J. Cryst. Growth 2004, 268, 568.
(9) Chakoumakos, B. C.; Arbraham, M.; Boatner, L. A. J. Solid State
Chem. 1994, 109, 197.

10.1021/cm061042a CCC: $37.00 © 2007 American Chemical Society

Published on Web 06/02/2007
(Y,Gd)(V,P)O4:Eu3+ as Potential Red-Emitting PDP Phosphor
Table 1. Crystallographic Data for YVO4, YPO4, GdVO4, and GdPO4
YVO4
cryst syst zircon tetragonal
space group I41/amd (no.141)
a (Å) 7.1183(1)
b (Å) 7.1183(1)
c (Å) 6.2893(1)
R (deg) 90
β (deg) 90
γ (deg) 90
point-group symmetry D4h
coordination no. Y(8); V(4); O(3)
refs 9 9, 22
become an important task for which research is being actively
pursued.
The crystal structure of MVO4 (M ) Y, Ce, Pr, Nd, Tb,
Ho, Er, Tm, Yb, Lu) of type zircon (ZrSiO4) was refined
with Rietveld analysis on the basis of neutron powder-
diffraction data by Chakoumakos et al.;9 these authors
discovered that MVO4 crystallizes in the tetragonal system
and can be described with space group I41/amd and Z ) 4,
in which M is noncentrosymmetrically coordinated by eight
oxygen atoms. Chakoumakos et al. reported also that the
V-O distance exhibits a small systematic decrease with
decreasing size of the M atom.9 As YVO4:Eu is known as a
typical red-emitting phosphor for which the host crystallizes
in a tetragonal structure, Wang et al. described the growth
and characterization of Y(V0.9P0.1)O4 crystals and confirmed
that Y(V0.9P0.1)O4 belongs to a ZrSiO4-type structure with
space group I41/amd; its lattice parameters were determined
to be a ) b ) 7.089(4) Å and c ) 6.253(2) Å.10 Rambabu
et al. investigated the synthesis, spectral characterization, and
influence of host matrix composition on the luminescence
and ambient decay lifetime of LnPO4:Eu (Ln ) Y, La, Gd)
phosphors under ultraviolet excitation.11 Sohn et al. reported
a search on the mixed compositional system of Eu3+-doped
Y(As,Nb,P,V)O4 for improved red-emitting phosphors using
a combinatorial method and discovered a phosphor with
optimal composition Y0.9(P0.92V0.03Nb0.05)O4:Eu3+ of which
the luminescence efficiency and Commission International
de I’Eclairage (CIE) color chromaticity at 147 nm excitation
is comparable with that of the conventional (Y,Gd)BO3:Eu3+
phosphor.12 Their results also indicated that the incorporation
of V or Nb in a small proportion into the YPO4 host matrix
acts as a bridge for energy transfer, thereby enhancing the
luminescence efficiency. They thus hinted that the route of
energy transfer under VUV excitation was from the Y-O
charge transfer (CT) to R-O CT in the RO43- (R ) V, Nb)
anion group and then to the Eu3+ center.12 These authors
also reported that only YPO4:Eu3+, not YVO4:Eu3+, exhibits
considerable emission upon VUV excitation. Minami et al.
described the fabrication and investigated the luminescence
properties of full-color thin films using (Y1-xGdx)VO4:R (R
) Eu, Er, Tm) phosphors.13 Zhang et al. reported a
(10) Wang, Y.; Lan, J.; Zhao, B.; Chen, J.; Lin, X.; Chen, J. J. Cryst.
Growth 2004, 263, 296.
(11) (a) Rambabu, U.; Buddhudu, S. Opt. Mater. 2001, 17, 401. (b) Ropp,
R. C. J. Electrochem. Soc. 1968, 115, 841.
(12) Sohn, K.-S.; Zeon, I. W.; Chang, H.; Lee, S. K.; Park, H. D. Chem.
Mater. 2002, 14, 2140.
(13) Minami, T.; Miyata, T.; Suzuki, Y.; Mochizuki, Y. Thin Solid Films
2004, 65, 469.
Chem. Mater., Vol. 19, No. 13, 2007 3279
YPO4 GdVO4 GdPO4
zircon tetragonal zircon tetragonal monoclinic
I41/amd (no.141) I41/amd (no.141) P121/n1(no.14)
6.8947(6) 7.2122(7) 6.6435(9)
6.8947(6) 7.2122(7) 6.8414(10)
6.0276(6) 6.346(2) 6.3281(6)
90 90
90 90 103.98(1)
90 90
D4h D4h P2
Y(8); P(4); O(3) Gd(8); V(4); O(3) Gd(8); P(4); O(3)
24 23
polyacrylamide gel synthesis at low temperature of nanoc-
rystalline YVO4:Eu, which exhibited greater luminescence
intensity than bulk YVO4:Eu.14 To investigate the mechanism
of luminescence and the role of Gd3+ in the energy transfer
under VUV excitation, Wang et al. concluded that energy
transfer occurs through the host lattice to Eu3+ via the overlap
between the charge transfer of Gd3+-O2- and the absorption
of the BO33- group in (Y,Gd)BO3:Eu under excitation at
100-300 nm.15 Yu et al. described the preparation of
nanocrystalline Y(V,P)O4:Eu and RVO4:Eu3+ thin films and
found that YVO4 and YPO4 form a complete solid solution
and that the x value in the Y(P1-xVx)O4:Eu3+ film has a great
influence on the luminescence intensity, color, and decay
behavior.16
To seek and develop satisfactory red-emitting PDP phos-
phors, we have thoroughly investigated the preparation and
photoluminescence (PL) under VUV excitation of several
modifications of Gd3+ and/or P5+-co-doped YVO4:Eu3+-
based phosphors and studied the spectral, optical, and
chromaticity properties of the obtained phosphors. Here, we
report the synthesis and VUV PL spectral investigations of
red-emitting (Y1-y-xGdyEux)(V1-zPz)O4 phosphors in several
series and investigated the dependence of luminescence
performance on phosphor composition. On analysis of the
VUV spectral and chromaticity investigations of these
phosphors, we achieved an optimized composition for a new
red-emitting phosphor with great potential for PDP applica-
tion. The luminescence and chromaticity characteristics of
(Y1-x-yGdy)(V1-zPz)O4:xEu are compared against a com-
mercial red-emitting phosphor (Y,Gd)BO3:Eu3+ as a refer-
ence. On the basis of these results, we evaluated the potential
application of (Y1-x-yEuxGdy)(V1-zPz)O4 as a red-emitting
PDP phosphor.
2. Experimental Section
2.1. Materials and Synthesis. We prepared polycrystalline
samples in two series with compositions (Y1-xEux)(V1-zPz)O4
(abbreviated Y(V1-zPz)O4:xEu3+) and (Y1-x-yEuxGdy)(V1-zPz)O4
(abbreviated (Y1-y-xGdy)(V1-zPz)O4:xEu) through solid-state reac-
tions. Briefly, the constituent oxides Y2O3 (99.99%), Gd2O3
(99.99%), Eu2O3 (99.99%), V2O5 (99.99%), and (NH4)2HPO4
(99.99%) (all from Aldrich Chemicals, Milwaukee, WI) were
intimately mixed in the requisite proportions. The mixtures were
(14) Zhang, H.; Fu, X.; Niu, X.; Sun, G.; Xin, Q. J. Solid State Chem.
2004, 177, 2649.
(15) Wang, Y.; Guo, X.; Endo, T.; Murakami, Y.; Ushirozawa, M. J. Solid
State Chem. 2004, 177, 2242.
(16) Yu, M.; Lin, J.; Wang, S. B. Appl. Phys. A 2005, 80, 353.
3280 Chem. Mater., Vol. 19, No. 13, 2007 Wu et al.

calcined at 600 °C with 5 mass % H3BO3 added as a flux, reground,

and sintered at four temperatures in a 1000-1300 °C range for 8
h to avoid possible incomplete reaction. The obtained product was
then checked with X-ray diffraction (XRD) for impurity phases. A
commercial PDP phosphor (Y,Gd)BO3:Eu3+ (Kasei Optonix, Ltd.,
Kanagawa, Japan, catalog No. KX-504) served as a reference for
comparison of VUV spectra and CIE chromaticity characteristics.
2.2. Material Characterizations. We verified the phase purity
of the phosphor samples as prepared by powder X-ray diffraction
(XRD) analysis with an advanced automatic diffractometer (Bruker
AXS D8) with Cu K radiation (λ ) 1.5418 Å) operating at 40 kV
and 20 mA. The XRD profiles were collected in a range 10° < 2θ
< 80°. Employing synchrotron radiation (SR) as a light source,
we examined the excitation (PLE) and photoluminescence (PL)
spectra excited with the vacuum ultraviolet (VUV) radiation. The
VUV spectra were measured in part with a PDP phosphor-testing
system (Zhejiang University Sensing Instruments Co., Ltd., China) Figure 1. Comparison of XRD profiles of (Y0.95-xGdxEu0.05)(V0.6P0.4)O4
equipped with VUV light sources (wavelengths 147 and 172 nm). with x ) (a) 0, (b) 0.2, (c) 0.4, (d) 0.6, (e) 0.8, and (f) 0.95 (synthesized at
For measurements with the synchrotron source, the intense and 1200 °C; 8 h).
continuous VUV beam was dispersed from a cylindrical grating
monochromator beam line coupled to the 1.5 GeV storage ring at calculation of GdVO4 and monoclinic GdPO4, respectively. The
the National Synchrotron Radiation Research Center in Taiwan; self-consistencies were performed on 18 and 45 k-points mesh in
this beam line has four gratings, and its focal length is 6 m. We the irreducible Brillouin zone for tetragonal (YPO4, YVO4, GdVO4)
used the 450 grooves/mm grating that spans the wavelength range and monoclinic (GdPO4) structures. The gap between valence and
100-350 nm. The emission from the phosphor was analyzed with core states is -6.0 Ry; convergence was assumed when the energy
a 0.32 m monochromator and detected with a photomultiplier in a difference between cycles was less than 0.0001 Ry.
photon-counting mode. We carefully normalized the incident
excitation sources and measured the PL signals from phosphors of 3. Results and Discussion
the same size; by this means, we quantitatively compared the
normalized PL spectra for separate samples. The Commission 3.1. Phase Characterizations and XRD Analysis. As
International de I’Eclairage (CIE) chromaticity coordinates for all summarized in Table 1, the host matrices of YPO4, YVO4,
samples were measured with a color analyzer (Laiko model DT- and GdVO4 crystallize in a tetragonal crystal system with
100) equipped with a CCD detector (Laiko Co., Tokyo, Japan). space group I41/amd, whereas GdPO4 crystallizes in a
Calculations of the electronic density of states were based on monoclinic system with space group P21/n (No. 14). To
density-functional theory (DFT). investigate the composition optimization of potential red-
2.3. Band Structure Calculations. To understand the effect of emitting phosphovanadate-based phosphors for PDP applica-
charge transfer on the VUV luminescence intensity in (Y,Gd)(V,P)-
tions, we have synthesized phosphors in several series with
O4:Eu3+ system, we used the full-potential linearized augmented-
plane-wave (LAPW)17-19 method to calculate the electronic struc-
compositions (Y1-xEux)(V1-zPz)O4, (Y1-yGdy)(V0.6P0.4)O4:
tures of YPO4, YVO4, GdPO4, and GdVO4 with the program Eu3+ and (Y1-yGdy)(V1-zPz)O4:Eu3+. Moreover, all chemical
WIEN2K.20 For GdMO4 (M ) P, V), the spin polarization compositions discussed in this work are nominal composi-
calculations were performed. The exchange and correlation energies tions.
were treated within the density-functional theory (DFT), with a A comparison of indexed XRD profiles for (Y1-xEux)VO4
generalized gradient approximation (GGA) for the exchange and with x ) 0, 0.01 0.03, 0.05, 0.07, and 0.09 (see the
correlation potential within the Perdew-Burke-Ernzerhof model.21 Supporting Information, Figure A) indicates that XRD
The truncation parameters for the basis set were Gmax ) 14 and patterns of Eu3+-doped YVO4 are consistent with that
Rmt × Kmax ) 7; Rmt is the smallest radius of an atomic sphere in
reported for YVO4 (JCPDS 76-1649) and no shifting of
the unit cell and Kmax is the magnitude of the largest k vector. The
diffraction features was observed with increasing proportion
atomic radii/bohr (1 bohr ) 0.529 × 10-10 m) values for Y, Gd,
V, P, and O are 1.48, 1.4, 1.7, 1.38, and 1.44, respectively. The of doped Eu3+; this observation is attributed to the similarity
self-consistencies were carried out on 18, 6, and 10 k-points mesh of ionic radii of Y3+ and Eu3+. Furthermore, a series of
in the irreducible Brillouin zone for tetragonal (YPO4, YVO4), spin indexed XRD profiles for (Y0.95Eu0.05)(V1-zPz)O4 with z )
0, 0.2, 0.4, 0.6, 0.8, and 1.0 (see the Supporting Information,
(17) Hohenberg, H.; Kohn, W. Phys. ReV. 1964, 136, B864. Figure B) were found to agree satisfactorily with those
(18) Kohn, W.; Sham, L. Phys. ReV. 1965, 140, A1133. reported for both YPO4 (JCPDS 84-0335) and YVO4 (JCPDS
(19) Singh, D. PlanewaVes, Pseudopotentials, and the LAPW Method;
Kluwer Academic: Boston, 1994. 76-1649). With the formation of a complete solid solution
(20) Blaha, P.; Schwarz, K.; Luitz, J. WIEN97, A Full Potential Linearized of (Y0.95Eu0.05)(V1-zPz)O4, we observed a systematic shifting
Augmented Plane WaVe Package for Calculating Crystal Properties;
Universität Wien: Vienna, Austria, 2000.
of diffraction angle 2θ toward greater angle direction when
(21) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. ReV. Lett. 1996, 77, z increases monotonically from 0 to 1.0. XRD profiles
3865. obtained from a series of (Y0.95-yGdyEu0.05)(V0.4P0.6)O4 with
(22) Milligan W. O.; Mullica; D. F.; Beall, G. W.; Boatner, L. A. Inorg.
Chim. Acta 1982, 60, 39. y ) 0, 0.2, 0.4, 0.6, 0.8, and 0.95 (synthesized at 1200 °C,
(23) Mullica, D. F.; David A. Grossie; Boatner, L. A. Inorg. Chim. Acta 8 h) are summarized in Figure 1. Formation of only a partial
1985, 109, 105.
(24) Donald F. Mullica; Sappenfield, E. L.; Abraham, M. M.; Chakouma- solid solution between Y(V0.6P0.4)O4 and Gd(V0.4P0.6)O4 is
kos, B. C.; Boatner, L. A. Inorg. Chim. Acta 1996, 248, 85 expected, as YVO4 (JCPDS 76-1649), GdVO4 (JCPDS 17-
(Y,Gd)(V,P)O4:Eu3+ as Potential Red-Emitting PDP Phosphor
Figure 2. VUV PL spectra of (Y1-xEux)VO4 (x ) 1, 3, 5, 7, and 9%): λex ) (a) 147 and (b) 172 nm (a, 5D0 f 7F1; b, 5D0 f 7F2; c, 5D0 f 7F3; d, 5D0 f
7F ).
4
Figure 3. VUV PL spectra of (Y0.95Eu0.05)(V1-zPz)O4 (z ) 0, 0.2, 0.4, 0.6, 0.8, 1.0): λex ) (a)147 and (b)172 nm (a, 5D0 f 7F1; b, 5D0 f 7F2; c, 5D0 f
7F ; d, 5D f 7F ).
3 0 4
0260), and GdPO4 (JCPDS 32-0386) are known to crystallize
in disparate structures, as indicated in Table 1. A careful
analysis of Figure 1 revealed that the XRD patterns shown
in Figures 1d-f cannot be completely indexed and become
increasingly complicated with increasing content of doped
Gd3+. When all Y3+ ions are replaced by Gd3+ ions, the peaks
that are indexed as GdPO4 (32-0386) appear (marked by
asterisk). The maximum proportion of Y to be replaced by
Gd was hence estimated to be ca. 0.8.
We calculated the lattice parameters on the basis of the
XRD patterns. In the tetragonal (Y0.95Eu0.05)(V1-zPz)O4 series
with z ) 0, 0.2, 0.4, 0.6, 0.8, and 1.0, lattice parameters a
() b) and c decreased with increasing content of P, which
we rationalize according to the fact that the radius of P is
smaller than that of V and that a solid solution is formed.
On the other hand, when increasing the content of Gd3+ in
(Y0.95-yGdyEu0.05)(V0.4P0.6)O4 with y ) 0, 0.2, 0.4, 0.6, 0.8,
and 0.95. Both lattice parameters a () b) and c increase when
Y3+ is increasingly replaced with Gd3+, which we rationalize
according to the fact that the radius of Gd3+ is larger than
that of Y3+.
3.2. Analysis of VUV Spectra. Shown in panels a and b
of Figure 3 are the VUV PL spectra of (Y1-xEux)VO4 under
excitation at 147 and 172 nm, respectively. As indicated in
Figure 2, the emission maxima of PL spectra for (Y1-xEux)VO4
Chem. Mater., Vol. 19, No. 13, 2007 3281
phosphors are attributed to the multiplet transitions 5D0 f
7F (J ) 1, 2, 3, 4) of Eu3+. In the absence of inversion
J
symmetry at the Eu3+ (or Y3+) lattice site, the electric-dipole
transition would dominate. As a result, the intensity of
electric-dipole allowed transitions 5D0 f 7F2,4 was much
stronger than that of magnetic-dipole allowed transitions 5D0
f 7F1,3. As indicated by the VUV PL spectra shown in Figure
2, the emission spectra of (Y1-xEux)VO4 (x ) 0.01, 0.03,
0.05, 0.07, 0.09) are mainly dominated by 5D0 f 7F2
regardless of the excitation wavelength. To optimize the
activator content doped in the host lattice, we measured the
emission intensity as a function of Eu3+ concentration relative
to Y3+. The intensity of transition 5D0 f 7F2 was found to
increase with increasing Eu3+ concentration. The content of
doped Eu3+ was hence maintained at 5% for all phosphor
samples discussed in the followings. The PL intensity was
found to decrease for a concentration of doped Eu3+ greater
than 5%, which is attributed to a concentration-quenching
effect. When the wavelength of excitation was altered from
147 to 172 nm, as shown in Figure 2b, the VUV PL spectra
resembled, in both shape and trend of the I-λ curve, those
obtained under excitation at 147 nm.
As the YPO4 host is reported to show strong absorption
in the VUV range,12 we have attempted to design a PDP
phosphor with great VUV efficiency by partly substituting
3282 Chem. Mater., Vol. 19, No. 13, 2007
Figure 4. Part of the energy level scheme of (a) YVO4:Eu and (b) YPO4:Eu. Excitation, emission, and energy-transfer processes are indicated.
V5+ by isovalent P to form phosphors in a series with normal
composition (Y0.95Eu0.05)(V1-zPz)O4. As indicated in Figure
3, the PL intensity of transition 5D0 f 7F2 attributed to
(Y0.95Eu0.05)(V1-zPz)O4 first increased with increasing z value
and then attained a maximum for samples with z ) 0.6 (λex
) 147 nm) and 0.4 (λex ) 172 nm), respectively. As a result,
the doping concentration of P was maintained at 40 mol %
for phosphors discussed in the following. Furthermore, the
PL intensity attributed to Eu3+ in (Y0.95Eu0.05)(V1-zPz)O4 was
discovered to decrease when the value of z exceeded the
maximum point (i.e., z ) 0.6; λex ) 147 nm).
As rationalized by Sohn et al.12 for the red-emitting YVO4:
Eu3+, upon VUV excitation, the energy is first absorbed by
the host lattice YVO4 through a charge-transfer mechanism,
which involves a transition between a 4d-like state of Y atom
and a 2p-like state of oxygen atom. The absorbed energy
was then transferred to VO43- groups, and eventually, to a
Eu3+ luminescence center and then relaxed as 5D0 f 7FJ
emission. Instead of transferring energy to Eu3+, the energy
may be relaxed to the ground state of the VO43- group
directly. But the relaxation process is less efficient than the
transition process in this case; the emission peak of VO43-
is hard to find. The whole process is illustrated in Figure
4a.25 The same as that in YVO4:Eu3+, the route of energy
transfer in YPO4:Eu3+ involves energy absorption by charge-
(25) Riwotzki, K.; Hasse, M. J. Phys. Chem. B 2001, 105,12709.
(26) Zeng, X.; Im, S.-J.; Jang, S.-H.; Kim, Y.-M.; Park, H.-B.; Son, S.-H.;
Hatanaka, H.; Kim, G.-Y.; Kim, S.-G. J. Lumin., 2006, 121,1.
Wu et al.
transfer mechanism involving Y3+-O2-. But the energy is
directly transferred to the Eu3+ center without passing the
PO43- group, as indicated in Figure 4b.25 As energy transfer
in YPO4 is inefficient, a VO43- group is required to act as a
bridge between the host absorption and the Eu3+ lumines-
cence center by the Y3+-O2- charge-transfer (CT) transition.
For this reason, the PL intensity of transition 5D0 f 7F2 was
observed to decrease when P was doped at a sufficiently
large proportion (i.e., z > 0.4) into the host lattice of
(Y0.95Eu0.05)(V1-zPz)O4.
The relative intensity of 5D0 f 7FJ multiplet emission is
also an important factor that determines the chromaticity or
saturation of red color; in general, the larger the magnitude
of ((5D0 f 7F2)/(5D0 f 7F1)) (R/O), the closer to the optimal
value of the color chromaticity. We also observed that the
R/O ratio decreased with increasing z value or increasing
P/V ratio, respectively. This observation can be rationalized
by the fact that the energy of the CT attributed to Eu3+-
O2- in phosphate, is too great to make the parity-forbidden
4f-4f transitions of Eu3+ acquire intensity from a charge-
transfer mechanism.12
Beyond investigating the partial substitution of V with P
to improve the PL efficiency, we also tried to co-dope Gd3+
into the Y3+-site of (Y0.95Eu0.05)(V0.4P0.6)O4, of which the
composition had been previously optimized, to form
(Y0.95-yGdyEu0.05)(V0.4P0.6)O4 phosphors in a series with
varied y value. Through the structural similarity of Y(V0.4P0.6)-
O4:Eu and (Y0.95-yGdy)(V0.4P0.6)O4:Eu, the VUV PL spectra
(Y,Gd)(V,P)O4:Eu3+ as Potential Red-Emitting PDP Phosphor
Figure 5. VUV PL spectra of (Y0.95-yGdyEu0.05)(V0.4P0.6)O4 (y ) 0, 0.2, 0.4, 0.6, 0.8, 0.95): λex ) (a)147 and (b)172 nm (a, 5D0 f 7F1; b, 5D0 f 7F2; c,
5D f 7F ; d, 5D f 7F ).
0 3 0 4
Figure 6. VUV PLE spectra of (Y0.75Gd0.2Eu0.05)(V0.4P0.6)O4 (solid line,
monitored at λem ) 619 nm), KX-504A (dashed line, monitored at λem )
592 nm), and (Y0.8Gd0.2)(V0.4P0.6)O4 host (dotted line, monitored at λem )
420 nm). The inset indicates VUV PL spectra excited at 147 nm.
have similar features except for the emission intensity.
Shown in Figure 5 is the dependence of doped Gd3+ content
on the PL intensity of 5D0 f 7F2 emission observed for
(Y0.95-yGdyEu0.05)(V0.4P0.6)O4 phosphors with y ) 0, 0.2, 0.4,
0.6, 0.8, 0.95, for which the PL intensity was observed to
increase abruptly when Gd at a small proportion (i.e., y )
0.2) was doped into the host. As part of the absorption band
of Gd3+ overlaps with the CT band from VO43- to the Eu3+
center, the Gd3+-doping produces more efficient excitation
in the Eu3+ center when Gd3+ is co-doped,8,16 but according
to the results presented in Figure 5, concentration quenching
is attributed to excessive doping of Gd3+ (i.e., y > 0.2) that
gradually imposes a detrimental effect on the VUV PL
intensity. The optimal dopant proportion of Gd3+ was thus
selected as 0.2 to form a composition (Y0.75Gd0.20Eu0.05)-
(V0.4P0.6)O4 that was adopted for the following spectral and
optical investigations.
To investigate the optical properties of (Y0.75Gd0.20)-
(V0.4P0.6)O4:Eu3+ with optimized composition, we measured
the VUV PL and PLE spectra for both pristine and Eu3+-
activated (Y0.8Gd0.20)(V0.4P0.6)O4 phosphors; the results appear
in Figure 6. In the upper left inset of Figure 6, only a broad
emission line spanning from 328 to 600 nm was observed,
attributed to emission of the VO43- group. When Eu3+ was
Chem. Mater., Vol. 19, No. 13, 2007 3283
Figure 7. VUV PL spectra of (Y0.75Gd0.2Eu0.05)(V0.4P0.6)O4 (solid line),
and commercial phosphors KX-504A (dash line): λex ) (a)147 and (b)172
nm.
doped into the host lattice to form (Y0.75Gd0.20)(V0.4P0.6)O4:
Eu3+, only emission signals of Eu3+ were observed as
indicated in Figure 5, which was attributed to energy transfer
from the VO43- group to the Eu3+ center, as already discussed
above. The PLE spectra presented in Figure 6 were measured
in the range 125-300 nm on monitoring the emissions
attributed to transitions 5D0 f 7F2 (Figure 6a) and VO43-
(Figure 6b). Charge-transfer transitions occur when a valence
electron transfers from the ligand to unoccupied orbitals of
the metal cation and are generally manifest through broad
absorption or emission in the VUV-UV spectral region. To
evaluate the performance and potential application of our
phosphors, we measured and compared the PL spectra
(Figure 7) of composition-optimized (Y0.75Gd0.20)(V0.4P0.6)-
O4:Eu3+ and a commercial red-emitting PDP phosphor KX-
504A excited by vacuum ultraviolet radiation at 147 and 172
nm, respectively. As shown in plots a and b of Figure 6, a
comparison of VUV PLE spectra for (Y0.75Gd0.20Eu0.05)-
(V0.4P0.6)O4 (monitored at λem ) 619 nm) and (Y0.8Gd0.20)-
(V0.4P0.6)O4 (monitored at λem ) 420 nm) reveals that several
CT absorption features attributed to PO43-, VO43-, and R3+-
O2- (R ) Y, Gd, Eu) have been identified. For instance, the
band appearing in the region from 164 to 190 nm (plots a
and b of Figure 6) is assigned to the CT transition between
Y3+ and O2-.16 This observation hints that the excitation
3284 Chem. Mater., Vol. 19, No. 13, 2007
Figure 8. DOS curves of (a) YPO4, (b) YVO4, (c) GdPO4, and (d) GdVO4. The first column shows the total DOS; the Fermi energy is the zero of the energy
scale.
energy is first absorbed by the host lattice involving the
transition between 4d-like states of Y and 2p-like states of
the oxygen atom. Then, the absorbed energy was transferred
to the anionic RO43- (R ) V, P) group, as suggested by
Wang et al.16 We thus observed one band in the spectral
region from 218 to 300 nm attributed to the CT transition
from the oxygen atom to the central V5+ ion of the VO43-
anion.13
As indicated by PLE spectra shown in Figure 6, the
absorption appearing at 178 nm is assigned to the Gd3+-
O2- CT transition that overlaps that attributed to the CT
transition of Eu3+-O2- at 196 nm, indicating that Eu3+
acquires energy from the Gd3+-O2- energy transfer.27 This
observation explains why the observed PL intensity is
significantly greater in (Y0.95-yGdyEu0.05)(V0.4P0.6)O4 phases
than those without Gd3+-co-doping. In Figure 6, we also
observed the CT transition of Eu3+-O2- at 196 nm and an
overlap between the CT transition bands of Gd3+-O2- and
Eu3+-O2-. We also noted that the intensities of both the
CT transition and the emission attributed to the transition
5
D0 f 7F2 under VUV excitation at 172 nm are greater than
that at 147 nm. The PL intensity of (Y0.75Gd0.20Eu0.05)-
(V0.4P0.6)O4 excited at 172 nm is much greater than that with
excitation at 147 nm.
Furthermore, as indicated by a comparison of VUV PL
spectra (Figure 7) measured at varied λex, we observed that
VUV absorption of (Y0.75Gd0.20Eu0.05) (V0.4P0.6)O4 is much
more intense than that of KX-504A. As indicated in Figure
7, under VUV excitation, the integrated peak area of our
phosphor (Y0.75Gd0.20Eu0.05)(V0.4P0.6)O4 is 55% (i.e., excited
at 147 nm) or 70% (i.e., excited at 172 nm) of that for KX-
504A. These observations hint that (Y0.75Gd0.20Eu0.05)(V0.4P0.6)-
O4 might serve as a promising substitute for KX-504A as a
red-emitting PDP phosphor as future optimization of sample
(27) Sato, Y.; Kumagai, T.; Okamoto, S.; Yamamoto, H.; Kunimoto, T.
Jpn. J. Appl. Phys. 2004, 43, 3456.
Wu et al.
preparation is completed. Tests of luminous efficiency on
phosphor powder and a PDP panel using our new phospho-
vanadate-based phosphors are currently in progress.
3.3. Results of Densities of States (DOS) Calculations.
The band calculations at the DFT level were employed to
calculate the electronic structure of RMO4 (R ) Y, Gd; M
) P, V) and understand its physical properties and inter-
atomic interactions. Figure 8 shows the total density of states
(DOS) and the projected DOS curves for (a) YPO4, (b)
YVO4, (c) GdPO4, and (d) GdVO4, respectively. The DOS
curve of YPO4 shows that the contributions of electronic
states near the valence (VB) and conduction bands (CB) are
dominated by the O(2p) and Y(4d) orbitals. The two features
between -15 and -10 eV consists mainly of the P-O
bonding states from P(3s, 3p) and O (2p) orbitals. The results
indicate that charge transfers from O(2p) to Y(4d) orbitals.
The DOS curve of YVO4 show varied orbital contributions
near the Fermi level (EF) compared to YPO4. As the V(3d)
orbital is located between Y(4d) and O(2p), orbital interac-
tions in these orbitals yield significant contributions of the
Y band in VB and CB. These results show that the valence
band about -10 to 0 eV consists mainly of O(2p), V(4s and
3d), and Y(4d) states that correspond to V-O and Y-O
bonding interactions. The orbital contribution of YVO4 above
EF is composed of V(3d, major), Y(4d, minor), and O(2p,
minor) orbitals. The calculated electronic structure indicates
that the charge transfer might occur not only in O(2p)-V(3d)
but also in O(2p)-Y(4d). The transition metal hence plays
a important role in improving the electron-transfer efficiently
to a rare-earth atom, consistent with the enhancement of the
optical transition in V-doped phases of the (Y,Gd)(V,P)O4:
Eu3+ system. For GdPO4, the density of states about EF are
dominated by the O(2p), Gd(5d) orbitals, and a sharp feature
at the Fermi level is contributed by localized Gd(4f) orbitals.
The 4f states contain occupied 4f peaks (spin down) and
unoccupied 4f peaks (spin up) separated by ca. 5 eV. There
(Y,Gd)(V,P)O4:Eu3+ as Potential Red-Emitting PDP Phosphor
Table 2. Comparison of CIE Chromaticity Coordinates of Phosphors (λex ) 172 nm)
phosphors x y
(Y0.99Eu0.01)VO4 0.6675 0.3270
(Y0.97Eu0.03)VO4 0.6705 0.3275
(Y0.95Eu0.05)VO4 0.6718 0.3275
(Y0.93Eu0.07)VO4 0.6735 0.3269
(Y0.91Eu0.09)VO4 0.6748 0.3262
(Y0.95Eu0.05)VO4 0.6718 0.3275
(Y0.95Eu0.05)(V0.8P0.2)O4 0.6691 0.3283
(Y0.95Eu0.05)(V0.6P0.4)O4 0.6651 0.3295
(Y0.95Eu0.05)(V0.4P0.6)O4 0.6572 0.3311
(Y0.95Eu0.05)PO4 0.5946 0.3393
is little, if any, contribution of Gd(5d) orbitals to the VB,
indicating that the bonding interaction between Gd and O
to be essentially ionic. These results indicate that charge
transfer in this phase is mostly from O(2p) to Gd(5d) orbitals
but internal charge transfer from Gd(4f) to Gd(5d) might
occur. The DOS plot of GdVO4 is essentially similar to that
of YVO4 except for an additional Gd(4f) orbital at the Fermi
level. Most contributions about the Fermi level are from
O(2p), V(3p, 3d), and Gd(5d) orbitals, indicating the bonding
interactions of Gd-O and V-O bonds. The 4f states are
made up of two peaks for spin down (occupied) and spin up
(unoccupied) levels, which are separated by ca. 4 eV. The
calculations suggest that the contribution of the filled Gd-
(4f) states is close to the Fermi level, which may enhance
the charge-transfer routes in O(2p)-V(3d) and O(2p)-Gd-
(5d), and f-d excitation. Our results are in consistent with
the observation that doping Gd3+ into the (Y,Gd)(V,P)O4:
Eu3+ system enhances the VUV luminescence intensity.
3.4 Investigations of Chromaticity Characteristics. For
practical applications, in addition to luminescence efficiency
and brightness, the color chromaticity is considered to be a
critical parameter for evaluation of the performance of PDP
phosphors. The CIE color coordinates (x,y) of all phosphors
investigated in this work are compared in Table 2. For
(Y1-xEux)VO4 phosphors in a series with varied Eu3+-dopant
content, the CIE (x,y) values were independent of the dopant
concentration. Moreover, for (Y0.95Eu0.05)(V1-zPz)O4 phos-
phors in a second series with varied content of P, our analysis
of (x,y) values indicates that x decreases as the concentration
of P dopant increases, whereas y increases, and the chro-
maticity shifts from pure red toward orange-red. As for co-
doping of Gd3+, both x and y decreased with increasing
concentration of doped Gd3+, but the range of shift upon
Gd3+-doping is too small and can be ignored. To understand
the dependence of chromaticity on the composition of dopant
P, we investigated the evolution of CIE chromaticity
coordinates for (Y0.95Eu0.05)(V1-zPz)O4 (z ) 0, 0.2, 0.4, 0.6,
1.0) as a function of z; the results are also summarized in
Table 2. With increasing z (from right to left), the x-
coordinate measured for (Y0.95Eu0.05)(V0.4P0.6)O4 decreased
Chem. Mater., Vol. 19, No. 13, 2007 3285
phosphors x y
(Y0.95Eu0.05)(V0.6P0.4)O4 0.6651 0.3295
(Y0.75Gd0.2Eu0.05)(V0.6P0.4)O4 0.6614 0.3286
(Y0.55Gd0.4Eu0.05)(V0.6P0.4)O4 0.6608 0.3286
(Y0.35Gd0.6Eu0.05)(V0.6P0.4)O4 0.6599 0.3282
(Y0.15Gd0.8Eu0.05)(V0.6P0.4)O4 0.6524 0.3262
(Gd0.95Eu0.05)(V0.6P0.4)O4 0.6338 0.3229
from 0.6719 (z ) 0) to 0.5946 (z ) 1.0) with the y-coordinate
remaining almost constant, indicating worse color saturation
in the red. The systematic evolution of the chromaticity
coordinate is considered to be related to the stronger VUV
absorption of YPO4 than that of YVO4 as discussed previ-
ously.13 These results show that our phosphors exhibit
superior color saturation. The experimental chromaticity
coordinates of red-emitting composition-optimized (Y0.75-
Gd0.20Eu0.05)(V0.4P0.6)O4 were studied against those for KX-
504A as a reference, and the color purity of (Y0.75Gd0.20-
Eu0.05)(V0.4P0.6)O4 is greater in the red than that of commercial
phosphor KX-504A.
4. Conclusions
We have prepared several series of red-emitting (Y,Gd)-
(V,P)O4:Eu3+ phosphors via a high-temperature, solid-state
route and investigated the synthesis, microstructure, and
luminescence properties of the red-emitting phosphors under
VUV excitation. We measured the VUV PL and PLE spectra
and chromaticity characteristics for the synthesized phos-
phors, and compared them with those of a commercial red-
emitting phosphor. Our research shows that using the 172
nm wavelength is more efficient than the 147 nm one in
pumping (Y,Gd)(V,P)O4:Eu3+ phosphors. The composition
of the new phosphor is optimized as (Y0.75Gd0.20Eu0.05)-
(V0.4P0.6)O4 and (Y,Gd)(V,P)O4:Eu3+ can hence serve as an
alternative phosphor to replace the widely used red-emitting
(Y,Gd)BO3:Eu3+ or Y2O3:Eu3+ commercial phosphors.
Acknowledgment. We appreciate generous financial support
from the National Science Council of Taiwan, R.O.C., under
Contracts NSC94-2113-M-009-001 and NSC95-2113-M-009-
024-MY3 and thank the members of Dr. B.-M. Cheng’s group
at NSRRC, Taiwan, for providing facilities and assistance with
VUV spectra measurements.
Supporting Information Available: Figures A and B (XRD
profiles) in PDF format. This material is available free of charge
via the Internet at http://pubs.acs.org.
CM061042A